JP6366134B2 - Cover for electromagnetic wave transmitter / receiver - Google Patents

Description

The present invention relates to a cover for an electromagnetic wave transmission / reception device in which a uniform metallic appearance without graininess is obtained using an organic compound.

In recent years, the appearance of automobile parts, automobile parts such as aluminum wheels and bumpers, electrical appliances such as smartphones, mobile phones, and personal computers has been required to have a high design, and a metallic gloss like a mirror surface has been imparted to the surface. The technology to do is demanded.

When giving such metallic gloss, for example, in automobiles, a so-called collision prevention system or the like, a radar device for distance measurement may be provided in each part of the automobile, for example, radiator grill, bumper, back panel, etc. . Since such a radar device irradiates an object with electromagnetic waves, receives a reflected wave from the object, and measures the distance, a material that shields and attenuates the electromagnetic waves between the radar device and the object (for example, metal) Etc.), the function cannot be fully exhibited. Therefore, the exterior parts of the automobile corresponding to the cover part of the radar device such as a radiator grill, a bumper, and a back panel positioned in front of the radar device are required to have electromagnetic wave transmission.

The same can be said for electrical appliances such as smartphones, mobile phones, personal computers, and portable games with communication functions. It is necessary to apply.

Conventionally, in order to impart a metallic gloss to the surface of an object, a paint containing a pigment using a metal powder such as aluminum or a pigment coated with a metal oxide such as titanium oxide or iron oxide on mica (so-called pearl pigment) In addition, metal plating or vapor deposition has been frequently used. However, all of the metallic coatings formed by these methods contain a metal, which is a conductor, and have the property of attenuating and shielding electromagnetic waves. Therefore, it is extremely difficult to apply to applications requiring electromagnetic wave transmission as described above. Met.

In addition, a technique for obtaining metallic luster using an organic material instead of the metal as described above has been studied. For example, in Patent Document 1, a thiophene weight having a distribution peak of weight average molecular weight in the range of 200 to 30000. Films with metallic luster containing coalescence have been reported.

However, since Patent Document 1 describes that this film has electrical conductivity, it suggests that this film has a property of attenuating and shielding electromagnetic waves. In general, conductive polymers such as polythiophene are considered to have electromagnetic wave shielding properties.

As means for avoiding these problems, for example, Patent Document 2 reports an electromagnetic wave-transmitting coating film having a glitter property in which a resin containing an oxazoline group and gold or silver nanoparticles are mixed.

However, in this method, most of the components that develop color tone are occupied by gold or silver that is valuable and expensive in terms of mineral resources, so that the production cost is extremely high compared to conventional metallic glossy means. Further, unless ultrafiltration is performed at the time of preparation to keep the particle size of the nanoparticles below a certain level, the electromagnetic wave permeability is rapidly lowered, so that the productivity is poor and the storability of the paint is poor.

In Patent Document 3, a radio wave transmitting decorative film is reported in which an alloy of silicon and metal is physically vapor-deposited on a plastic film such as acrylic or polycarbonate, and a plastic film is thermally laminated on the vapor deposition surface. Yes.

However, this method requires large-scale equipment, and it is necessary to install the base material in a vacuum or decompressed container, and there is room for improvement in that it is difficult to apply to a large base material. In addition, the method of forming a metal layer by physical vapor deposition such as sputtering requires strict film thickness control, so there is room for improvement in that productivity is lowered.

In Patent Document 4, a coating material containing a flat glittering material made of aluminum (hereinafter referred to as an aluminum pigment) and a flat non-conductive pigment is prepared, and the number of glittering materials in the coating film overlapped. There has been reported a coating material that exhibits electromagnetic wave permeability by satisfying a predetermined relationship between the distance between the luminescent material and the glitter material.

However, with this method, there is room for improvement in that it is difficult to obtain stable electromagnetic wave transmission because the spacing between aluminum pigments is likely to vary depending on the coating conditions of equipment such as spray and spin coating that are commonly used for painting. is there. In order to control the distance between the aluminum pigments to a constant distance, the coating film thickness and the drying conditions are limited, and 10 μm or more is required to obtain a sufficient metallic gloss film. This method also requires a pigment dispersion step. Furthermore, the following points are mentioned as fundamental and important issues. That is, since a metal pigment such as aluminum settles in the paint due to its specific gravity, it needs to be stirred regularly during use. The aluminum pigment is easily crushed by the stirring force, and the crushed fine particles are aggregated to form irregular shaped aggregated particles, which lowers electromagnetic wave permeability. For this reason, it is extremely difficult to industrially realize a coating film that maintains a uniform spacing between aluminum pigments as described in Patent Document 4.

International Publication No. 2014/021405 Japanese Patent No. 5163715 Japanese Patent No. 5346632 Japanese Patent No. 5237713

The problem to be solved by the present invention is to provide a cover for electromagnetic wave transmission / reception equipment having uniform metallic gloss without graininess and high electromagnetic wave permeability and excellent productivity.

As a result of diligent research to solve the above-mentioned problems, the present inventors have used a coating liquid containing a polythiophene having a specific substituent on the thiophene ring as a coloring material that exhibits a metallic luster. A coating film having high electromagnetic wave permeability with no uniform metallic gloss is obtained, and by applying the coating liquid on a non-metallic substrate, uniform metallic gloss and high electromagnetic wave without graininess It has been found that a cover for electromagnetic wave transmission / reception equipment having transparency can be obtained with high productivity, and the present invention has been completed.

（式中のＲ^１は水素原子、アルコキシ基、アミノ基又はヒドロキシル基を表し、Ｒ^２はアルコキシ基、アミノ基又はヒドロキシル基を表す。また、ｎは３〜１００の整数を表す。） That is, this invention has a nonmetallic base material and the coating film formed by apply | coating the coating liquid containing the polythiophene represented by following General formula (1) on the said nonmetallic base material. An electromagnetic wave transmitting / receiving device cover characterized by the above is provided.

(In the formula, R ¹ represents a hydrogen atom, an alkoxy group, an amino group, or a hydroxyl group, R ² represents an alkoxy group, an amino group, or a hydroxyl group. N represents an integer of 3 to 100.)

The electromagnetic wave transmitting / receiving device cover of the present invention has a coating film formed by coating a coating liquid on a non-metallic substrate, and the coating liquid contains the above polythiophene, A metallic gloss can be developed without using a metallic pigment. In addition, since the polythiophene can be dissolved in an organic solvent or water by an anionic dopant to be described later, it is not a metallic gloss with a granular feeling like a metallic pigment, but a uniform metal plating like metal plating. A metallic gloss can be obtained. Further, therefore, the pigment dispersion process is not required for the preparation of the coating liquid, and no particle size control technique and dispersion equipment are required. Moreover, since the coating film in this invention shows the outstanding permeability | transmittance with respect to both an electric field and a magnetic field, and is formed on a nonmetallic base material, the cover for electromagnetic wave transmission / reception apparatuses of this invention does not have a graininess. Not only uniform metallic gloss but also high electromagnetic wave transparency can be expressed. Further, since the polythiophene used in the present invention does not aggregate like the metallic pigment, the obtained metallic gloss does not decrease with time, and stable electromagnetic wave permeability can be obtained. In addition, since the coating liquid used in the present invention uses the above-described polythiophene that is an organic compound, when used in paints, gravure inks, inkjet inks, etc., there is a difference in specific gravity from other components contained in the paints. Since it is less than metallic pigments and does not settle, it is excellent in storage stability, does not require stirring during use, and does not impair electromagnetic wave permeability. In addition, since the polythiophene used in the present invention itself exhibits electromagnetic wave permeability, there is no limitation on the coating method of the coating liquid used in the present invention, and large facilities for manufacturing the electromagnetic wave transmitting / receiving device cover of the present invention. Is unnecessary. Furthermore, since the coating film according to the present invention provides high concealability even when the film thickness is, for example, about 1 μm, the electromagnetic wave transmitting / receiving device cover of the present invention is an expensive pigment (for example, multi-layer printing or high concealment) No pigments made of aluminum).

Due to the above-described features, the electromagnetic wave transmitting / receiving device cover of the present invention includes automotive exterior parts such as radiator grills, bumpers, and back panels; automobiles such as dashboards, instrument panels, and door trims. It can be suitably used for interior parts such as: housings of household electrical appliances such as refrigerators, televisions, microwave ovens, and air conditioners and remote controllers thereof; housings of information terminals such as mobile phones, smartphones, and notebook computers.

It is the schematic of the cross section of the cover for electromagnetic wave transmission / reception apparatuses which concerns on embodiment of this invention. It is the schematic of the cross section of the cover for electromagnetic wave transmission / reception apparatuses which concerns on suitable embodiment of this invention.

（式中のＲ^１は水素原子、アルコキシ基、アミノ基又はヒドロキシル基を表し、Ｒ^２はアルコキシ基、アミノ基又はヒドロキシル基を表す。また、ｎは３〜１００の整数を表す。） FIG. 1 shows an outline of a cross section of an electromagnetic wave transmitting / receiving device cover according to an embodiment of the present invention.
As shown in FIG. 1, the electromagnetic wave transmitting / receiving device cover of the present invention includes a non-metallic substrate 10 and a polythiophene represented by the following general formula (1) (hereinafter abbreviated as “substituted polythiophene (1)”). And a coating film 11 formed by applying a coating solution containing a non-metallic substrate 10.

(In the formula, R ¹ represents a hydrogen atom, an alkoxy group, an amino group, or a hydroxyl group, R ² represents an alkoxy group, an amino group, or a hydroxyl group. N represents an integer of 3 to 100.)

However, in each repeating unit of the substituted polythiophene (1), the mutual positional relationship between R ¹ and R ² is not particularly limited, and even if all the repeating units have the same positional relationship between R ¹ and R ^2. Alternatively, in at least one repeating unit appropriately selected, the positions of R ¹ and R ² represented by the general formula (1) may be reversed.

In general, polythiophene is considered to have electrical conductivity and electromagnetic shielding properties, but the substituted polythiophene (1) exhibits electromagnetic wave transmissivity against such conventional technical common sense. This is because the molecular weight of the substituted polythiophene (1) is relatively small, and the range of the number of repeating units n is 3 to 100, and preferably 3 to 40.

Electromagnetic wave transmission / reception device of the present invention including the coating film 11 and the nonmetallic substrate 10 after the coating film 11 is formed on the nonmetallic substrate 10. The electric field and magnetic field transmittance of the entire cover for use is not particularly limited, but it is preferably 90% or more, more preferably 95% or more, at least at either 700 MHz or 900 MHz. By setting it to 90% or more, the electromagnetic wave transmission property of the cover for an electromagnetic wave transmission / reception device of the present invention can be improved in each of the above-described applications, and such characteristics are exhibited by the substituted polythiophene (1). be able to. The upper limit is not particularly limited, but is preferably close to 100% from the same viewpoint.

The thickness of the coating film 11 is not particularly limited, but is preferably in the range of 0.5 to 30 μm and more preferably in the range of 1 to 10 μm in view of electromagnetic wave permeability, coating film appearance, and the like.

（式中のＲ^１は水素原子、アルコキシ基、アミノ基又はヒドロキシル基を表し、Ｒ^２はアルコキシ基、アミノ基又はヒドロキシル基を表す。） The substituted polythiophene (1) is a polymer in which three or more molecules of a substituted thiophene compound represented by the following general formula (2) (hereinafter abbreviated as “substituted thiophene compound (2)”) are bonded to each other. is there.

(In the formula, R ¹ represents a hydrogen atom, an alkoxy group, an amino group or a hydroxyl group, and R ² represents an alkoxy group, an amino group or a hydroxyl group.)

In the substituted thiophene compound (2), R ¹ is a hydrogen atom, an alkoxy group, an amino group or a hydroxyl group, and R ² is an alkoxy group, an amino group or a hydroxyl group, but R ¹ is preferably a hydrogen atom. , R ² is preferably an alkoxy group. In synthesizing the substituted polythiophene (1), the substituted thiophene compound (2) as a raw material thereof can be used alone or in combination of two or more. In addition, when using two types of substituted thiophene compounds (2), the arrangement | sequence of a monomer is not specifically limited, A substituted polythiophene (1) is any of a random copolymer, an alternating copolymer, or a block copolymer. It may be.

In the substituted thiophene compound (2), when either R ¹ or R ² or both are alkoxy groups, the alkyl chain preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of the substituted thiophene compound (2) having an alkoxy group include 3-methoxythiophene, 3-ethoxythiophene, 3-propoxythiophene, 3-isopropoxythiophene, 3-butoxythiophene, 3,4-dimethoxythiophene, 3 , 4-diethoxythiophene, 3-methoxy-4-ethoxythiophene, 3,4-dipropoxythiophene and the like.

In the substituted thiophene compound (2), when either R ¹ or R ² or both are amino groups, specific examples of the substituted thiophene compound (2) include 3-aminothiophene, 3,4-diaminothiophene, 3- (N-methylamino) thiophene, 3- (N, N-dimethylamino) thiophene, 3- (N-ethylamino) thiophene, 3- (N, N-diethylamino) thiophene, 3- (N, N- Propylamino) thiophene,-(N, N-dibutylamino) thiophene, 3,4-bis (N, N-dimethylamino) thiophene, 3,4-bis (N, N-diethylamino) thiophene and the like.

In the substituted thiophene compound (2), when R ¹ is other than a hydrogen atom and the types of substituents of R ¹ and R ² are different, specific examples of the substituted thiophene compound (2) include 3-amino-4-methyl Examples include thiophene, 3-amino-4-hydroxythiophene, 3-methyl-4-hydroxythiophene, 3-methoxy-4-aminothiophene, 3-methoxy-4-methylthiophene, 3-methoxy-4-hydroxythiophene, and the like. .

N in the general formula (1) representing the substituted polythiophene (1) represents the number of repeating units having the substituted thiophene compound (2) as a unit, and the range thereof is 3 to 100. In order to obtain a more excellent metallic-tone coating film 11, the number of repeating units n is preferably in the range of 3-40.

The substituted polythiophene (1) can be produced by a chemical polymerization method or an electrolytic polymerization method using the substituted thiophene compound (2) as a raw material. The “chemical polymerization method” in the present invention is a method in which a substituted thiophene compound (2) and an oxidizing agent are added in the presence of a solvent, and polymerization is carried out in the liquid phase, the solid phase, the interface between the liquid phase and the solid phase, or both phases. Say the method. The “electrolytic polymerization method” is a method in which a substituted thiophene compound (2) and an electrolyte are added in the presence of a solvent, platinum, gold, or the like is used as an anode, platinum, nickel, or the like is used as a cathode. It is a method in which polymerization is performed on an electrode by inserting it into the electrode and applying a voltage to the electrolyte.

The oxidant used in the chemical polymerization method and the electrolyte used in the electrolytic polymerization method can be the same, and various metal salts can be used. Examples of the metal salt include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, tantalum, Tungsten, rhenium, osmium, iridium, platinum, cerium, neodymium and other metal fluoride salts, chloride salts, bromide salts, iodide salts, ammonium salts, sulfates, hypochlorites, chlorates, perchlorates Acid salt, permanganate, chromate, dichromate, phosphate, citrate, tartrate, oxalate, paratoluenesulfonate, hexafluorophosphate, tetrafluoroborate, etc. Can be mentioned. Among these, iron (III) perchlorate and iron (III) chloride are preferable.

In the production of the substituted polythiophene (1), an oxidizing agent used in the chemical polymerization method or an anion derived from the electrolyte used in the electrolytic polymerization method may be introduced into the polythiophene skeleton as a dopant. This dopant interacts with and stabilizes the cationic site in the polythiophene skeleton, and when the coating liquid is applied / printed, the molecular orientation of the substituted polythiophene (1) is promoted on the surface of the coating film 11, It becomes easier to obtain a metallic gloss. Thus, it is preferable that said coating liquid is what anion was doped with respect to substituted polythiophene (1).

The solvent used in the chemical polymerization method is preferably one in which the substituted thiophene compound (2) is sufficiently dissolved, and the solvent used in the electrolytic polymerization method is preferably one in which the substituted thiophene compound (2) and the electrolyte are sufficiently dissolved. Further, since the polymerization reaction proceeds on the surface of the oxidant even in a state where the oxidant is not sufficiently dissolved, the solvent used in the chemical polymerization method may not be a solvent in which the oxidant is sufficiently dissolved. Those that are sufficiently soluble are preferred. Specific examples of the solvent used in the chemical polymerization method and the electrolytic polymerization method include methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate, normal propyl acetate, hexane, heptane, toluene, xylene, cyclohexanone, dichloromethane, chloroform, carbon tetrachloride, Examples include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, acetonitrile, nitromethane, γ-butyrolactone, and propylene carbonate. These solvents can be used alone or in combination of two or more.

In addition, the amount of the substituted thiophene compound (2) and the oxidizing agent used in the chemical polymerization method and the amount of the substituted thiophene compound (2) and the electrolyte used in the electrolytic polymerization method are further promoted in the molecular orientation of the substituted polythiophene (1). Since metallic gloss is more easily obtained, the range of 0.25 to 15 moles of oxidant or electrolyte is preferable with respect to 1 mole of substituted thiophene compound (2), and more preferably 0.5 to 10 moles.

The substituted polythiophene (1) obtained by the above chemical polymerization method or electrolytic polymerization method is obtained by precipitation in the reaction solution as a colored solid. The precipitated substituted polythiophene (1) is obtained by filtration and washing, and then recovered through a drying process such as drying under reduced pressure. The obtained substituted polythiophene (1) is dissolved in a solvent according to the characteristics required for each application such as paint, gravure ink, inkjet ink, etc. (for example, drying speed, environment / toxicity to human body) A working solution is obtained.

It is preferable that said coating liquid contains 0.05-15 mass% of substituted polythiophenes (1). The coating liquid is appropriately prepared according to the characteristics required for each application, but the effects of the present invention are sufficiently obtained within the above range.

The electromagnetic wave transmitting / receiving device cover according to the present invention can be used for a cover portion of an electromagnetic wave transmitting / receiving device (device capable of transmitting and / or receiving electromagnetic waves, for example, a radar device for distance measurement and a transmitting / receiving device for radio waves for communication). If it is a thing, it will not specifically limit, However, Automotive exterior parts, such as a radiator grille, a bumper, and a back panel; Automotive interior parts, such as a dashboard, an instrument panel, a door trim; Refrigerator, TV, microwave oven, air conditioner, etc. A housing for home appliances and a remote controller thereof; a housing for an information terminal such as a mobile phone, a smartphone, or a notebook computer is preferable.

Although the coating method of said coating liquid is not specifically limited, It is preferable to apply as a metallic paint, a metallic gravure ink, or a metallic inkjet ink.

When using said coating liquid as a metallic paint, as a composition of each component in a metallic paint, substituted polythiophene (1) 0.25-15 mass parts, vehicle 10-50 mass parts, solvent 50-90 masses, for example. Part and other additives and 5 parts by mass or less.

Examples of the vehicle include acrylic resin, epoxy resin, polysiloxane resin, maleic acid resin, vinyl resin, polyamide resin, nitrocellulose, cellulose acetate, ethyl cellulose, ethylene-vinyl acetate copolymer, urethane resin, polyester resin, and alkyd. Examples thereof include resins. These vehicles can be used alone or in combination of two or more. Here, in order to obtain a metallic-tone coating film, the coating liquid does not use a metallic pigment that requires a vehicle to form a coating film, but instead uses a substituted polythiophene (1) having self-film forming properties. A vehicle is not necessarily required for use. When no vehicle is used, the composition of each component in the metallic paint is, for example, 0.25 to 10 parts by weight of substituted polythiophene (1), 90 to 99.5 parts by weight of solvent, and 5 parts by weight or less of other additives. What is done.

Examples of the solvent include water; alcohol solvents such as ethanol, isopropyl alcohol, n-butanol, iso-butanol, and tert-butanol; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; methyl acetate, acetic acid Ethyl, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, 2 -Ester solvents such as ethyl methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate; aprotic such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile Polar solvents; ether solvents such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol-n-propyl ether, propylene glycol-n-butyl ether, propylene glycol monomethyl ether acetate Propylene glycol such as propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate and ester compounds thereof; diglyme solvents such as diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether; halogen solvents such as trichloroethane and chloroform; cyclics such as tetrahydrofuran and dioxane Ether solvent; Zen, toluene, aromatic solvents such as xylene. These solvents can be used alone or in combination of two or more.

Examples of the other additives include pigment dispersants, antifoaming agents, thickeners, leveling agents, ultraviolet absorbers, light stabilizers, antibacterial agents, antifungal agents, preservatives, and waxes. These additives can be used alone or in combination of two or more.

Examples of the coating method when the above coating liquid is used as a metallic paint include a roll coater, a comma coater, a knife coater, a curtain coater, a shower coater, a spin coater, dipping, screen printing, spraying, an applicator, a bar coater, and the like. Is mentioned. The coating liquid is preferably diluted with the solvent in order to obtain an appropriate viscosity according to these coating methods.

Examples of the non-metallic base material 10 in the case where the above coating liquid is used as a metallic paint include a plastic base material, a glass base material, various building materials, and a rubber base material. Among them, a plastic base material is preferable.

The resin used as the material for the plastic substrate may be a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include polyvinyl chloride, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer, polymethyl methacrylate, polyvinyl alcohol, polyvinylidene chloride, General-purpose plastics such as polyethylene terephthalate; Engineering plastics such as polyamide, polyacetal, polycarbonate, polyphenylene ether, polybutylene terephthalate, ultra-high molecular weight polyethylene (U-PE), polyvinylidene fluoride; polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate , Polyamideimide, polyetherimide, polyetheretherketone, polyimide, liquid crystal polymer, Super engineering plastics such as Li and polytetrafluoroethylene. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester, epoxy resin, silicone resin, polyurethane resin, and the like. The shape of the plastic base material made of these resins may be a molded one, a film or a sheet.

Examples of the glass substrate include float plate glass. Moreover, as said various building materials, a slate board, a calcium silicate board, a slag gypsum board, a mortar board etc. are mentioned, for example.

Examples of the material of the rubber base include butadiene rubber, chloroprene rubber, chlorosulfonated polyethylene, ethylene / propylene diene rubber, fluoro rubber, butyl rubber, natural rubber, silicone rubber, urethane rubber, and the like. The shape of these rubber substrates may be a molded one or a film or a sheet.

When the nonmetallic substrate 10 is a plastic substrate, a primer may be applied in advance to the surface of the plastic substrate in order to improve the adhesion of the coating film 11 to the plastic substrate. Examples of the primer include a primer using a two-component curable urethane resin, a fluororesin, an epoxy resin, an aqueous urethane resin, and the like.

FIG. 2 shows an outline of a cross section of the electromagnetic wave transmitting / receiving device cover according to the preferred embodiment of the present invention.
As shown in FIG. 2, a topcoat layer 12 may be provided on the coating film 11 in order to improve the durability of the coating film 11. The thickness of the top coat layer 12 is preferably in the range of 5 to 50 μm and more preferably in the range of 10 to 30 μm in consideration of the coating film appearance, scratch resistance, weather resistance and the like. Examples of the resin used for the coating material for the top coat layer 12 include petroleum resins, chlorinated ethylene-vinyl acetate copolymer resins, fluororesins, ethylene-vinyl acetate copolymer resins, polyester resins, cellulose resins, and polyamides. Resin, nitrified cotton, vinyl resin, acrylic resin and the like can be mentioned. Among these, the top coat layer 12 is preferably a cured coating film of an active energy ray curable resin composition. Examples of the active energy ray-curable resin composition include, as a main component, various active energy ray-curable oligomers / monomers such as unsaturated polyester, acrylic, vinyl ether, maleimide, and epoxy, and a reactive diluent. , Polymerization initiators, polymerization accelerators, organic solvents and the like may be blended and mixed as necessary. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays, among which ultraviolet rays are preferable.

As one aspect of the electromagnetic wave transmitting / receiving device cover of the present invention, one obtained by printing the coating liquid on the non-metallic substrate 10 by gravure printing can be mentioned. When using said coating liquid as metallic gravure ink, as composition of each component in metallic gravure ink, for example, substituted polythiophene (1) 0.25-10 mass parts, vehicle 5-40 mass parts, solvent 50- 90 mass parts and what is comprised by 5 mass parts or less of other additives are mentioned.

Examples of the vehicle include tall oil rosin, gum rosin, wood rosin, lime rosin, rosin ester, maleic acid resin, vinyl resin, polyamide resin, nitrocellulose, cellulose acetate, ethyl cellulose, ethylene-vinyl acetate copolymer, urethane resin, polyester. Resins, alkyd resins, acrylic resins and the like can be mentioned. As these vehicles, those dissolved in a solvent and those dispersed in a solvent can be used. These vehicles can be used alone or in combination of two or more. Here, as in the case where the above coating liquid is used as a metallic paint, a vehicle is not necessarily required. Therefore, when a vehicle is not used, the composition of each component in the metallic gravure ink is, for example, substituted polythiophene (1) Examples include 0.25 to 10 parts by mass, 90 to 99.5 parts by mass of solvent, and 3 parts by mass or less of other additives.

As the solvent and other additives used when the above coating liquid is used as a metallic gravure ink, the same solvents as those used as the above metallic paint can be used.

Among the covers for electromagnetic wave transmission / reception equipment of the present invention, those by gravure printing are those obtained by gravure printing on the non-metallic substrate 10 using the above coating liquid as a metallic gravure ink. As the non-metallic substrate 10 when the above coating liquid is used as a metallic gravure ink, a plastic film substrate is suitable. Examples of the plastic film substrate include polyethylene film, ethylene-vinyl acetate copolymer film, polypropylene film, polyethylene terephthalate film, nylon film, polyvinyl chloride film, polyvinylidene chloride film, and ethylene-vinyl alcohol copolymer film. , Polystyrene film, polyacrylonitrile copolymer film; film obtained by co-extruding a plurality of resins used in these films; film coated with a resin such as polyvinylidene chloride to provide barrier properties based on these films A film on which an inorganic compound such as silica or alumina is vapor-deposited.

When using the above coating liquid as a metallic gravure ink and performing gravure printing on a plastic film substrate, a primer is previously applied to the surface of the plastic film substrate in the same manner as when using the above metallic coating. It may be left. Moreover, you may provide the topcoat layer 12 similarly on the coating film 11 obtained by carrying out gravure printing of said coating liquid. When the above coating liquid is used as a metallic gravure ink, the thickness of the topcoat layer 12 is preferably in the range of 0.5 to 20 μm in consideration of the coating film appearance, scratch resistance, weather resistance, and the like. The range of 10 μm is more preferable.

As one aspect of the electromagnetic wave transmitting / receiving device cover of the present invention, one obtained by printing the above coating liquid on the non-metallic substrate 10 by ink jet printing can be mentioned. When using said coating liquid as metallic inkjet ink, as composition of each component in metallic inkjet ink, substituted polythiophene (1) 0.05-7.5 mass part, vehicle 1-10 mass part, solvent The thing comprised by 85-98 mass parts and 5 mass parts or less of other additives is mentioned. When the composition of each component is within this range, a coating film having a more excellent metallic feeling can be obtained, and the ejection stability of ink from the nozzle head of the inkjet printer can be further stabilized.

As said vehicle, the same thing as the case where said coating liquid is used as metallic gravure ink can be used. Further, as in the case of using the above coating liquid as a metallic paint and a metallic gravure ink, a vehicle is not necessarily required. Therefore, when a vehicle is not used, the composition of each component in the metallic inkjet ink is, for example, a substituted polythiophene (1) 0.05 to 7.5 parts by mass, 90 to 99.5 parts by mass of solvent, and 5 parts by mass or less of other additives may be mentioned. When the composition of each component is within this range, a coating film having a more excellent metallic feeling can be obtained, and the ejection stability of ink from the nozzle head of an ink jet printer can be further stabilized.

As the solvent used when the above coating liquid is used as a metallic inkjet ink, it is preferable to use a solvent having wettability for the purpose of preventing the ink from drying, in addition to water. As the wettable solvent, those which are miscible with water and can prevent clogging of the head of an ink jet printer are preferable. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less , Propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, Examples include mesoerythritol and pentaerythritol. These solvents can be used alone or in combination of two or more. The content of the wet solvent in the metallic inkjet ink is preferably in the range of 3 to 50% by mass.

Furthermore, it is preferable to add a solvent having a function of improving the permeability to the nonmetallic substrate 10 and adjusting the dot diameter on the nonmetallic substrate 10. Examples of such solvents include lower alcohols such as ethanol and isopropyl alcohol; ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether; propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether and the like. It is done. Similarly, these solvents can be used alone or in combination of two or more. The content of such a solvent in the metallic inkjet ink is preferably in the range of 0.01 to 10% by mass.

Examples of other additives used when the coating liquid is used as a metallic inkjet ink include surfactants added to adjust ink characteristics such as surface tension. Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Among these, anionic surfactants and nonionic surfactants are preferable.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, higher alcohol. Examples include sulfates and sulfonates of ethers, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc. Specific examples of these include dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, dibutylphenylphenol dis Acid salts, and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid. Esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, fatty acid alkylol amides, alkyl alkanol amides, acetylene glycol, oxyethylene adducts of acetylene glycol And polyethylene glycol polypropylene glycol block copolymer. Among these, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid alkyl Roll amide, acetylene glycol, oxyethylene adduct of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymer are preferred.

As surfactants other than the above, silicone surfactants such as polysiloxane oxyethylene adducts; fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers Agents: Biosurfactants such as spicrispolic acid, rhamnolipid, and lysolecithin can also be used.

The above surfactants can be used alone or in combination of two or more. Moreover, since the solubility stability etc. of surfactant improve, it is preferable that the HLB (Hydrophile-Lipophile Balance) value is the range of 7-20. Further, the addition amount in the case of adding the surfactant is preferably in the range of 0.001 to 2% by mass, more preferably in the range of 0.001 to 1.5% by mass in the total amount of the ink, and 0.01 to 1 A range of mass% is more preferred.

Further, as other additives other than the above-mentioned surfactants, preservatives, viscosity modifiers, pH adjusters, chelating agents, plasticizers, antioxidants, ultraviolet absorbers, etc. may be added as necessary. it can.

The surface tension of the metallic inkjet ink is preferably in the range of 20 to 60 mN / m, more preferably in the range of 20 to 45 mN / m, and more preferably in the range of 20 to 40 mN / m because the printability in the inkjet printer is further improved. A range is further preferred.

Further, the viscosity of the metallic inkjet ink is preferably in the range of 1.2 to 20 mPa · s, more preferably in the range of 2 to 15 mPa · s, since the discharge stability in the inkjet printer is further improved. The surface tension and viscosity of the metallic ink-jet ink can be set within the above-mentioned preferred ranges by adjusting the type and addition amount of the surfactant and water-soluble solvent to be blended.

Among the covers for electromagnetic wave transmission / reception equipment of the present invention, those by ink jet printing are ink jet prints on the non-metallic substrate 10 using the above coating liquid as a metallic ink jet ink. As the non-metallic substrate 10 when the above coating liquid is used as a metallic inkjet ink, a plastic film substrate or a plastic substrate, a glass substrate, various building materials, a rubber substrate and the like are suitable. As said plastic film base material, the same thing as the case where said coating liquid is used as said metallic gravure ink is mentioned, for example. Examples of the plastic base material, the glass base material, the various building materials, and the rubber base material include those similar to those used when the coating liquid is used as the metallic paint. These shapes may be molded, film or sheet.

When using the above coating liquid as a metallic inkjet ink and performing inkjet printing on a plastic film substrate, a primer is preliminarily applied to the surface of the plastic film substrate in the same manner as when used as the metallic paint and metallic gravure ink. A primer layer may be provided by coating. Examples of the primer layer include a coating film or a cured coating film such as a two-component curable urethane resin, a water-based urethane resin, a water-based acrylic resin, and an active energy ray-curable vinyl monomer. Moreover, you may provide the topcoat layer 12 similarly on the coating film 11 obtained by carrying out inkjet printing of said coating liquid. When the above coating liquid is used as a metallic inkjet ink, the thickness of the top coat layer 12 is preferably in the range of 0.5 to 10 μm in consideration of the appearance of the coating film, scratch resistance, weather resistance, and the like. The range of 5 μm is more preferable.

Hereinafter, the present invention will be described in more detail with reference to specific examples. In addition, the weight average molecular weight (Mw) of a polymer is measured on condition of the following by gel permeation chromatography (GPC).

[GPC measurement conditions]
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: N-methylpyrrolidone Flow rate: 1.0 mL / min Injection volume: 100 μL (sample concentration 4 mg / mL tetrahydrofuran solution)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

(1) Preparation of coated material [gravure print]
The gravure ink composition was printed on a biaxially stretched polyethylene terephthalate film (Toyobo Co., Ltd. “E5100”, thickness 12 μm; hereinafter referred to as “PET film”) at a printing speed of 40 meters per minute using a Helio 175 wire solid plate. And a biaxially stretched polypropylene film (“Pyrene P2161” manufactured by Toyobo Co., Ltd., thickness: 20 μm; hereinafter abbreviated as “OPP film”) with a thickness of 2 μm, respectively. Dry at 80 ° C.

[IJ ink printed matter]
The ink jet ink composition is an ink jet printer having a piezo head having a maximum driving frequency of 7.6 KHz and a resolution of 360 DPI (360 dots per 25.4 mm), with a film thickness of 1 μm on the corona surface treatment surface of the PET film and the OPP film. Printed and dried at 80 ° C.

[Paint application]
The coating composition is applied to a polyethylene terephthalate plate (thickness 2 mm; hereinafter abbreviated as “PET plate”) and a polycarbonate plate (thickness 2 mm; hereinafter abbreviated as “PC plate”) using air spray. Each was coated with a film thickness of 5 μm, allowed to stand at room temperature for 10 minutes, and then dried at 80 ° C.

(2) Evaluation method of coated material [Gloss value]
Using a PET film or a PET plate as the base material, the gloss of the coated product obtained by the above-described method is 60 degrees with an incident angle of 60 degrees and a reflection angle of 60 degrees with a gloss meter ("micro-TRI-gloss" manufactured by BYK Gardner). Measurements were taken at 5 arbitrary points, and the average value was recorded.

[Appearance of coating film]
A PET film or a PET plate was used as the base material, and the following items were visually evaluated with respect to the appearance of the coated product obtained by the method described above.
(Background concealment)
○: The base is completely hidden.
Δ: The base is slightly transparent.
X: The base is clearly transparent and the base material type can be visually discriminated.
(Specular reflection of coating film)
○: Recognize even the details of mirror images without image distortion and blurring.
Δ: Although the image is slightly distorted and blurred, the shape of the mirror image can be recognized.
X: The image is severely distorted and blurred, and the mirror image cannot be recognized.
(Coating grain feeling)
○: There is no graininess like the plated surface.
Δ: A very fine granular pattern is visible.
×: Clearly grainy.

[Electromagnetic wave transmission]
Using a PET film or a PET plate as a substrate, the electromagnetic wave transmission characteristics of the coated product obtained by the above-described method were measured using two types of KEC method and free space method.

The KEC method is a near field electric field shielding effect and magnetic field shielding effect measurement method that evaluates electromagnetic wave transmission from the signal intensity difference before and after an electromagnetic wave of an arbitrary frequency transmitted from a signal generator passes through a sample. is there. Specifically, electric field and magnetic field transmittances at frequencies of 100 MHz, 500 MHz, 700 MHz, 900 MHz, and 1 GHz were measured. At this time, the electromagnetic wave transmittance (%) was determined based on the calculation formula of (transmitted signal intensity) / (incident signal intensity) × 100 = (electromagnetic wave transmittance).

The free space method is a method in which a plane wave is made incident on a sheet-like sample using a horn antenna or a derivative lens, and the reflected wave intensity or transmitted wave intensity from the sample is measured to evaluate electromagnetic wave permeability. Specifically, an electromagnetic wave having a frequency of 76 GHz corresponding to the W band was incident on the sample, and the transmittance was measured from the intensity difference between the incident wave and the transmitted wave. At this time, the electromagnetic wave transmittance (%) was determined based on the calculation formula of (transmitted signal intensity) / (incident signal intensity) × 100 = (electromagnetic wave transmittance).

[Adhesion of gravure prints]
A cellophane tape (“Cello Tape” manufactured by Nichiban Co., Ltd., 18 mm width) is applied to the coated surface of the gravure printed matter obtained by the above method, and 10 seconds after the application, the tape is peeled off at 180 ° direction at a speed of 10 mm per second. A peel test was conducted. The surface of the coated material after the test was converted into electronic data with a scanner having a resolution of 300 dpi, and the peeled area / cello tape area = the coating film peeling ratio (%) was calculated. The smaller this value, the stronger the adhesion between the ink coating film and the film. This value is preferably 30% or less and more preferably 15% or less in each film.

[Adhesion of inkjet printed matter]
A cellophane tape (18 mm width “Cello Tape” manufactured by Nichiban Co., Ltd.) is applied to the coated surface of the ink-jet printed matter obtained by the above-mentioned method, and after 10 seconds, the cellophane tape is peeled off at 180 ° direction at a speed of 10 mm per second, and a peel test is performed. went. The surface of the coated product after the test was converted into electronic data using a scanner with a resolution of 300 dpi, and the peeled area / cello tape area = coating film peeling ratio [%] was calculated. The smaller this value, the stronger the adhesion between the ink coating film and the film. This value is preferably 30% or less and more preferably 20% or less in each film.

[Primary adhesion of paint coatings]
10 × 10 cuts are made with a cutter knife at 1 mm square on the coating film surface of the coating material obtained by the above-mentioned method, and a peel test using cellophane tape (“Cello Tape” manufactured by Nichiban Co., Ltd., 18 mm width) is performed. The number of remaining eyes was evaluated according to the following criteria.
○: 86-100 pieces Δ: 60-85 pieces ×: 59 pieces or less

(3) Coating liquid evaluation method [sedimentation stability]
Each composition was placed in a glass sample bottle, the lid was closed, allowed to stand at room temperature, allowed to stand for 6 hours, and the degree of sedimentation of the pigment after standing for 24 hours was visually observed.
○: No pigment precipitation was observed after 24 hours.
Δ: Pigment sedimentation was not observed after 6 hours, but pigment sedimentation was confirmed after 24 hours.
X: Pigment sedimentation was confirmed after 6 hours.

[Storage stability]
Each composition was measured for viscosity with an E-type viscometer (“TV-20 type” manufactured by Toki Sangyo Co., Ltd.), then placed in a glass sample bottle, sealed and closed at 60 ° C. Left in the tank. After 30 days, the sample bottle was taken out from the thermostat and the viscosity of the ink was measured. Evaluation was judged as follows.
○: Change rate of viscosity is less than 10%.
Δ: Viscosity change rate is 10% or more and less than 20%.
X: Viscosity change rate is 20% or more, or ink separation occurs.

<Synthesis Example 1>
To an Erlenmeyer flask having a volume of 50 ml, 6.5 g of iron (III) perchlorate and 7.3 g of acetonitrile were added as oxidizing agents, and stirred to prepare a 1 M concentration solution. Next, 1.0 g of 3-methoxythiophene and 12.8 g of acetonitrile are added to a 100 ml three-necked flask equipped with a nitrogen introduction tube and an Allen cooling tube, and the flask is immersed in an ice bath while introducing nitrogen gas into the liquid. The solution was stirred for 30 minutes to prepare a 0.5M concentration solution. Thereafter, the ice bath was removed, and the temperature of the solution was raised to 20 ° C. Then, the above-mentioned 1M-iron (III) perchlorate acetonitrile solution was poured into a three-necked flask and reacted at 20 ° C for 4 hours. After completion of the reaction, the resulting solution was filtered through a Kiriyama funnel, and the residue was washed with methanol to remove the oxidizing agent. The residue obtained after washing was vacuum-dried to obtain a blue-violet solid of polythiophene compound (S-1) exhibiting metallic luster in a yield of 80%. The weight average molecular weight Mw of the polythiophene compound (S-1) was 1,600, and the number of repeating units was about 15.

<Synthesis Example 2>
To an Erlenmeyer flask with a capacity of 50 ml, 9.5 g of iron (III) chloride and 4.3 g of acetonitrile were added as oxidizing agents, and stirred to prepare a 2M concentration solution. Next, 1.0 g of 3-methoxythiophene and 12.8 g of acetonitrile are added to a 100 ml three-necked flask equipped with a nitrogen introduction tube and an Allen cooling tube, and the flask is immersed in an ice bath while introducing nitrogen gas into the liquid. The solution was stirred for 30 minutes to prepare a 0.5M concentration solution. Thereafter, the ice bath was removed, and the temperature of the solution was raised to 50 ° C. Then, the above-mentioned 2M-iron (III) chloride solution was poured into a three-necked flask and reacted at 50 ° C for 4 hours. After completion of the reaction, the resulting solution was filtered through a Kiriyama funnel, and the residue was washed with methanol to remove the oxidizing agent. The residue obtained after washing was vacuum-dried to obtain a blue-violet solid of polythiophene compound (S-2) exhibiting metallic luster with a yield of 75%. The weight average molecular weight Mw of the polythiophene compound (S-2) was 1,400, and the number of repeating units was about 13.

<Example 1>
1 g of the polythiophene compound (S-1) obtained in Synthesis Example 1 is dissolved in a mixed solvent composed of 70 g of acetonitrile and 29.6 g of methyl ethyl ketone, and the rheology control agent (“BYK-” manufactured by BYK Chemie Co., Ltd.) is stirred while the solution is stirred. 410 ”) and 0.1 g of an antifoaming agent (“ Dappo SN-368 ”manufactured by San Nopco Corporation) were added to obtain a metallic gravure ink composition (A-1). The gravure ink printed matter (AP-1) was obtained by coating and printing this by the above-mentioned method.

<Example 2>
Primer (“Univia NT K1 Medium” manufactured by DIC Graphics Co., Ltd.) was added to Zahn Cup No. 3 using a diluent solvent (“Reducer No. 3K” manufactured by DIC Graphics Co., Ltd.). Dilute to 3-15 seconds viscosity. The diluted primer solution was coated / printed in the same manner as the above gravure ink coating / printing method, and the metallic gravure ink composition (A-1) obtained in Example 1 after drying the primer coating film Was coated and printed by the method described above. This obtained the gravure ink printed matter (AP-2) which consists of two layers of primer / gravure ink.

<Example 3>
Primer (“Univia NT K1 Medium” manufactured by DIC Graphics Co., Ltd.) was added to Zahn Cup No. 3 using a diluent solvent (“Reducer No. 3K” manufactured by DIC Graphics Co., Ltd.). Dilute to 3-15 seconds viscosity. The diluted primer solution was coated / printed in the same manner as the above gravure ink coating / printing method, and the metallic gravure ink composition (A-1) obtained in Example 1 after drying the primer coating film Was coated and printed by the method described above. Next, the top coat ("ULTIMA Z OP varnish" manufactured by DIC Graphics Co., Ltd.) was added to the Zahn Cup No. 3 using a diluting solvent ("Reducer No. 3K" manufactured by DIC Graphics Co., Ltd.). Dilute to 3-15 seconds viscosity. This diluted topcoat solution is coated and printed on the above-mentioned (A-1) layer in the same manner as the above-described gravure ink coating and printing method, and three layers of primer / gravure ink / topcoat The gravure ink printed matter (AP-3) which consists of was obtained.

<Example 4>
1 g of the polythiophene compound (S-2) obtained in Synthesis Example 2 is dissolved in 99.2 g of water, and 0.1 g of rheology control agent (“BYK-420” manufactured by BYK Chemie) is added to this solution while stirring. 0.2 g of a foaming agent (“SN deformer 777” manufactured by San Nopco Co., Ltd.) and 0.5 g of a leveling agent (“BYK-348” manufactured by Big Chemie) were added to obtain a metallic gravure ink composition (A-2). By applying and printing this by the above-mentioned method, a gravure ink printed matter (AP-4) was obtained.

<Example 5>
The primer (“SF Primer No. 930” manufactured by DIC Graphics Co., Ltd.) was added to the Zahn Cup No. 3 using a diluent solvent (“Reducer No. 3K” manufactured by DIC Graphics Co., Ltd.). Dilute to 3-15 seconds viscosity. The diluted primer solution was coated / printed in the same manner as the above-described gravure ink coating / printing method, and the metallic gravure ink composition (A-2) obtained in Example 4 after drying the primer coating film Coated and printed. This obtained the gravure ink printed matter (AP-5) which consists of two layers of primer / gravure ink.

<Comparative Example 1>
Solvent-based back-printed gravure ink ("Univia LT Silver K1" manufactured by DIC Graphics Corporation) is referred to as metallic gravure ink composition (B-1), and diluted solvent ("Reducer No. 3K" manufactured by DIC Graphics Corporation). Zahn cup no. Dilute to 3-15 seconds viscosity. This solution was coated and printed by the above-described method to obtain a gravure ink print (BP-1).

<Comparative example 2>
Water-based back-printed gravure ink (“Marine Plus G Silver (K3)” manufactured by DIC Graphics Co., Ltd.) is referred to as metallic gravure ink composition (B-2), and diluted solvent (“Water Resistant” manufactured by DIC Graphics Co., Ltd.). Using Juicer No. 3 ”), Dilute to a viscosity of 3-18 seconds. This solution was applied and printed by the method described above to obtain a gravure ink print (BP-2).

Said evaluation was performed about the metallic gravure ink composition obtained by said Examples 1-5 and Comparative Examples 1-2, and the printed matter using them.

Table 1 shows a summary of the composition of gravure ink printed materials and the results of evaluation when the coating liquid of the present invention is used as gravure ink.

<Example 6>
A mixed solvent of 5 g of propylene glycol, 3 g of 1,3-butanediol and 89.8 g of water was prepared, and 1 g of the polythiophene compound (S-2) obtained in Synthesis Example 2 was dissolved therein. Further, 1.2 g of a leveling agent (“Surfinol 485” manufactured by Nissin Chemical Industry Co., Ltd.) was added while stirring this solution to obtain a metallic ink for water-based inkjet recording (A-6). This was coated / printed by the above-described method to obtain an ink-jet printed matter (AP-6).

<Example 7>
A mixed solvent consisting of 15 g of propylene glycol, 10 g of 1,3-butanediol, and 64.9 g of water was prepared, and 1 g of the polythiophene compound (S-2) obtained in Synthesis Example 2 was dissolved therein. While stirring this solution, 8.6 g of acrylic resin (“Boncoat WKA-565” manufactured by DIC Corporation) and 0.5 g of a leveling agent (“Surfinol 485” manufactured by Nissin Chemical Industry Co., Ltd.) were added, and an aqueous inkjet was added. A metallic ink for recording (A-7) was obtained. This was coated / printed by the above-described method to obtain an inkjet printed matter (AP-7).

<Example 8>
A mixed solvent consisting of 15 g of propylene glycol, 10 g of 1,3-butanediol and 63.5 g of water was prepared, and 1 g of the polythiophene compound (S-2) obtained in Synthesis Example 2 was dissolved therein. Further, while stirring this solution, 10 g of a polyolefin resin (“Hardlen NA-3002” manufactured by Toyobo Co., Ltd.) and 0.5 g of a leveling agent (“Surfinol 485” manufactured by Nissin Chemical Industry Co., Ltd.) are added, for aqueous inkjet recording. A metallic ink (A-8) was obtained. This was coated and printed by the above-described method to obtain an ink-jet print (AP-8).

<Comparative Example 3>
Vapor-deposited aluminum pigment ("Metaseen 41-0310" manufactured by BASF, 2-methoxy-1-methylethyl acetate dispersion having an aluminum content of 10% by mass), an ultrasonic oscillator ("US-300T" manufactured by NSK Ltd.) ) To obtain an aluminum pigment dispersion having an average particle diameter (D50) of 6.0 μm and an average thickness of 20 nm. To 20 g of this dispersion, 15 g of propylene glycol, 10 g of 1,3-butanediol, 45.9 g of water, 8.6 g of an acrylic resin (“Boncoat WKA-565” manufactured by DIC Corporation) and a leveling agent (Nisshin Chemical Industry Co., Ltd.) “Surfinol 485”) 0.5 g was added to obtain an aqueous inkjet recording metallic ink (B-3). This was coated / printed by the above-mentioned method to obtain an ink-jet print (BP-3).

Said evaluation was performed about the inkjet ink obtained by said Examples 6-8 and the comparative example 3, and printed matter using them.

Table 2 shows a summary of the configuration of ink-jet prints and the evaluation results when the coating liquid of the present invention is used as an ink-jet ink.

<Example 9>
A primer is prepared by mixing 40 g of an acrylic resin (“Acridic 56-1155” manufactured by DIC Corporation), 30 g of an aromatic organic solvent (“Solvesso 100” manufactured by TonenGeneral Sekiyu KK), and 30 g of butyl acetate. did. This was coated / printed in the same manner as the above-described metallic paint coating / printing method. Next, 1.5 g of the polythiophene compound (S-1) obtained in Synthesis Example 1 is dissolved in a mixed solvent consisting of 18 g of acetonitrile and 80 g of N-methylpyrrolidone, and the leveling agent (Big Chemie) is stirred while the solution is stirred. 0.5 g of “BYK-348” manufactured by the company was added to obtain a metallic paint (A-9). This was coated and printed on the above-mentioned primer coating layer by the above-mentioned method, to obtain a metallic coating product (AP-9) composed of two layers of primer layer / metallic coating layer.

<Example 10>
A mixed solvent consisting of 47.5 g of N-methylpyrrolidone and 12.5 g of acetonitrile was prepared, and 1 g of the polythiophene compound (S-1) obtained in Synthesis Example 1 was dissolved therein. Further, while stirring this solution, 40 g of an acrylic resin (“Acridic 56-1155” manufactured by DIC Corporation) was added to obtain a metallic paint (A-10). This was coated and printed by the method described above. Next, ethyl acetate / normal butyl acetate / propylene glycol monomethyl ether acetate = 20/70/10 was added as a thinner for dilution to 100 g of an ultraviolet curable resin (“Unidic V-4025” manufactured by DIC), and the solution viscosity was Iwata. A top coat solution was prepared by diluting in a cup until 12 seconds. This is coated / printed in the same manner as the above-described metallic paint coating / printing method, and then irradiated with an ultraviolet ray with a dose of 0.8 J / cm ² using a high-pressure mercury lamp with an output of 80 W / cm. It performed and obtained the metallic paint (AP-10) containing the topcoat layer by ultraviolet curing.

<Example 11>
80 g of aqueous acrylic resin (“Boncoat EM-400” manufactured by DIC Corporation), 19.7 g of dipropylene glycol-n-butyl ether, and 0.5 g of a leveling agent (“BYK-348” manufactured by Big Chemie) were mixed and stirred. Primers were prepared. This was coated / printed in the same manner as the above-described metallic paint coating / printing method. Next, 1.5 g of the polythiophene compound (S-2) obtained in Synthesis Example 2 was dissolved in 98.0 g of water, and a leveling agent (“BYK-348” manufactured by BYK-Chemie) was added while stirring the solution. .5 g was added to obtain a metallic paint (A-11). By coating and printing this on the above-mentioned primer coating layer by the above-mentioned method, the metallic coating material (AP-11) which consists of two layers of a primer layer / metallic coating layer was obtained.

<Example 12>
A mixed solvent consisting of 10 g of dipropylene glycol-n-butyl ether and 48.5 g of water was prepared, and 1 g of the polythiophene compound (S-1) obtained in Synthesis Example 1 was dissolved therein. Further, while stirring this solution, 40 g of an aqueous acrylic resin (“Boncoat EM-400” manufactured by DIC Corporation) and 0.5 g of a leveling agent (“BYK-348” manufactured by Big Chemie) were added, and a metallic paint (A-12 ) This was coated and printed by the method described above. Next, 0.5 g of a leveling agent “BYK-348” (manufactured by Big Chemie) is mixed with 100 g of an ultraviolet curable resin (“Unidic WNS-232” manufactured by DIC Corporation) to prepare a topcoat solution. did. This is coated / printed in the same manner as the above-described metallic paint coating / printing method, and then irradiated with an ultraviolet ray with a dose of 0.8 J / cm ² using a high-pressure mercury lamp with an output of 80 W / cm. It performed and obtained the metallic paint (AP-12) containing the topcoat layer by ultraviolet curing.

<Comparative example 4>
4.67 g of aluminum pigment (“TCR-3040” manufactured by Toyo Aluminum Co., Ltd.), 3.88 g of aluminum pigment (“SAP 550N” manufactured by Showa Aluminum Powder Co., Ltd.), acrylic resin (“ACRICID 56-1155” manufactured by DIC Corporation) 33.6 g, 10 g of xylene, 20 g of an aromatic organic solvent (“Solvesso 100” manufactured by TonenGeneral Sekiyu KK) and 31.7 g of butyl acetate were mixed to obtain a metallic paint (B-4). This was coated and printed by the method described above. Next, ethyl acetate / normal butyl acetate / propylene glycol monomethyl ether acetate = 20/70/10 as a thinner for dilution was added to 100 g of an ultraviolet curable resin (“Unidic V-4025” manufactured by DIC Corporation), and the viscosity of the solution was increased. Was diluted with an Iwata cup until 12 seconds to prepare a topcoat solution. This is coated / printed in the same manner as the above-described metallic paint coating / printing method, and then irradiated with an ultraviolet ray with a dose of 0.8 J / cm ² using a high-pressure mercury lamp with an output of 80 W / cm. It performed and obtained the metallic paint (BP-4) containing the topcoat layer by ultraviolet curing.

<Comparative Example 5>
Mix and knead 5.0 g of aluminum pigment (“STAPA Hydrolan 2194” manufactured by Eckert), 5.0 g of diethylene glycol dimethyl ether, and 0.5 g of pigment dispersant (“Disparlon AQ-330” manufactured by Enomoto Chemical Co., Ltd.) A paste was prepared. 10.0 g of this aluminum paste is 55.6 g of an aqueous acrylic resin (“Bernock WD-551” manufactured by DIC Corporation), 0.2 g of a leveling agent (“BYK-348” manufactured by BYK Chemie), and a leveling agent (Nisshin Chemical Co., Ltd.) 0.6 g of “Surfinol 104DPM” manufactured by the company, 0.4 g of antifoaming agent (“BYK-011” manufactured by Big Chemie), and 0.3 g of a rheology control agent (“BYK-425” manufactured by Big Chemie) were mixed. A base metallic paint was prepared. Further, 5.8 g of water-dispersed polyisocyanate (“Bernock DNW-5500” manufactured by DIC Corporation) and 10 g of water were added to 70 g of the main metallic coating material to obtain a two-component curable metallic coating material (B-5). This was coated and printed by the above-mentioned method to obtain a metallic paint (BP-5). However, in this comparative example, drying was performed at 23 ° C. for 7 days after coating.

<Comparative Example 6>
Electromagnetic wave permeability was evaluated without applying anything to an aluminum-deposited polyethylene terephthalate film (“VM-PET 1510” manufactured by Toray Film Processing Co., Ltd., film thickness: 12 μm). In addition, since the coating material is not applied, the gloss value and the coating film appearance are not evaluated.

Said evaluation was performed about the metallic paint obtained in said Examples 9-12 and Comparative Examples 4-5, and those coating materials.

Table 3 shows a summary of the composition of the metallic paint and the evaluation results when the coating liquid of the present invention is used as a metallic paint.

From the evaluation results shown in Tables 1 to 3, it was confirmed that the coating liquid in the present invention can be sufficiently used as a metallic gravure ink, a metallic inkjet ink, and a metallic paint. In addition, by coating and printing these on a non-metallic substrate, it is possible to form a metallic coating film equivalent to a uniform metal plating without graininess on the substrate to be printed and the object to be coated. It was also confirmed that permeability could be imparted. Therefore, it was confirmed that these printed materials and coated materials can be sufficiently used as a cover for an electromagnetic wave transmitting / receiving device.

On the other hand, it was confirmed that the coating liquids of Comparative Examples 1 to 5 using a metallic pigment were inferior in sedimentation stability and storage stability. In addition, by applying and printing the coating liquids of Comparative Examples 1 to 5 on a non-metallic substrate, a metallic design can be obtained on the printed material and the coated material, but the metallic tone has a granular feeling. Only gloss was obtained, and only low electromagnetic wave permeability was obtained. Comparative Example 6 provided almost no electromagnetic wave permeability because it was provided with an aluminum vapor deposition film.

10: Non-metallic substrate 11: Coating film 12: Topcoat layer

Claims (6)

A non-metallic substrate;
A cover for electromagnetic wave transmission / reception equipment, comprising: a coating film formed by coating a coating liquid containing polythiophene represented by the following general formula (1) on the non-metallic substrate.

(In the formula, R ¹ represents a hydrogen atom, an alkoxy group, an amino group, or a hydroxyl group, R ² represents an alkoxy group, an amino group, or a hydroxyl group. N represents an integer of 3 to 100.) The electromagnetic wave transmitting / receiving device cover according to claim 1, wherein the electromagnetic wave transmitting / receiving device cover has an electric field and a magnetic field transmittance of 90% or more at least in either one of 700 MHz and 900 MHz. The electromagnetic wave transmitting / receiving device cover according to claim 1, wherein the non-metallic substrate is a plastic substrate. The electromagnetic wave transmitting / receiving device cover according to any one of claims 1 to 3, wherein the coating liquid is one in which anions are doped into the polythiophene. The cover for electromagnetic wave transmission / reception equipment according to any one of claims 1 to 4, wherein the coating liquid contains 0.05 to 15% by mass of the polythiophene. The electromagnetic wave transmitting / receiving device cover according to any one of claims 1 to 5, further comprising a topcoat layer on the coating film.

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